Determination of seventeen major and trace elements in new float glass standards for use in forensic comparisons using laser ablation inductively coupled plasma mass spectrometry.

Consensus concentration values for seventeen (17) major and trace elements typically present in soda-lime glass manufactured using the "float " process and used in the quantitative analysis and forensic comparison of glass samples were determined using laser ablation (LA) micro sampling coupled to inductively coupled plasma mass spectrometry (ICP-MS). This is the first reporting of the chemical characterization of a new set of float glass intended for use as matrix-matched calibration standards in the forensic analysis and comparison of glass by LA-ICP-MS using a standard test method (ASTM E2927-16e1). Three Corning Float Glass Standards (CFGS) were manufactured at low, medium, and high concentrations of 32 elements typically encountered in float glass samples as found in forensic casework. This work describes an international collaboration among seven (7) laboratories to evaluate the homogeneity of the three glass materials and reports the consensus concentrations values of 17 elements at three concentration levels. Eight (8) sets of independent results from LA-ICP-MS analysis using the standard test method of analysis and one set of micro-X-ray Fluorescence Spectrometry (µXRF) data (using method ASTM E2926-17) resulted in typically <3% relative standard deviation (RSD) within each lab and < 5% RSDs among all labs participating in the study for the concentration ranges using sampling spots between 50 µm - 100 µm in diameter. These results suggest that the new calibration standards are homogeneous for most elements at the small sampling volumes (~ 90 µm deep by ~80 µm in diameter) reported and show excellent agreement among the different participating labs. Consensus concentration values are determined using a previously reported calibration standard (FGS 2) and checked with a NIST 1831 SRM®. A collaboration with National Institute of Standards and Technology (NIST) scientists to certify these glasses as SRMs, including the certification of the quantitative analysis of the minor and trace element content, for future distribution by NIST is ongoing.

An interlaboratory study evaluating the interpretation of forensic glass evidence using refractive index measurements and elemental composition.

Seventeen laboratories participated in three interlaboratory exercises to assess the performance of refractive index, micro X-ray Fluorescence Spectroscopy (µXRF), and Laser Induced Breakdown Spectroscopy (LIBS) data for the forensic comparison of glass samples. Glass fragments from automotive windshields were distributed to the participating labs as blind samples and participants were asked to compare the glass samples (known vs. questioned) and report their findings as they would in casework. For samples that originated from the same source, the overall correct association rate was greater than 92% for each of the three techniques (refractive index, µXRF, and LIBS). For samples that originated from different vehicles, an overall correct exclusion rate of 82%, 96%, and 87% was observed for refractive index, µXRF, and LIBS, respectively. Special attention was given to the reporting language used by practitioners as well as the use of verbal scales and/or databases to assign a significance to the evidence. Wide variations in the reported conclusions exist between different laboratories, demonstrating a need for the standardization of the reporting language used by practitioners. Moreover, few labs used a verbal scale and/or a database to provide a weight to the evidence. It is recommended that forensic practitioners strive to incorporate the use of a verbal scale and/or a background database, if available, to provide a measure of significance to glass forensic evidence (i.e., the strength of an association or exclusion).

Development of tailor-made inorganic gunshot residue (IGSR) microparticle standards and characterization with a multi-technique approach.

The forensic analysis of inorganic gunshot residues (IGSR) involves analytical measurements from samples taken from skin and other substrates. The standard practice for IGSR analysis recommends the use of Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) to identify the gunshot residues using combined information of the particle's morphology and elemental composition. However, the current deficit on IGSR standard reference materials (SRM) limits the optimization of SEM-EDS for modern, lead-free ammunition and the development of emerging analytical techniques. This study aims to enhance existing capabilities by producing tailor-made microparticle suspensions that can be used for the quality control of GSR analysis, validation of existing and emerging methods, interlaboratory testing, and systematic transfer and persistence studies. To fill this gap, IGSR microparticle standards were developed by discharging various leaded and lead-free primers under controlled conditions and creating suspensions in an organic medium, then evaluated for homogeneity and stability of morphology and elemental composition. The IGSR microparticles suspensions were evaluated by three analytical techniques-SEM-EDS, Laser-Induced Breakdown Spectroscopy (LIBS) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) -to characterize the elemental composition and particle morphology. The ICP-MS digestion method was validated for these novel IGSR microparticle suspensions, and figures of merit and ruggedness testing are reported. The standard demonstrated stability in its dry and suspension forms, providing versatility for use in multiple types of analytical methods and substrates. This research is anticipated to assist forensic and environmental scientists by providing IGSR standards that can strengthen research, expand access to new detection techniques, and enhance laboratories' cross-validation and quality assurance.

Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by µ-XRF, ICP-MS, and LA-ICP-MS.

Elemental analysis of glass was conducted by 16 forensic science laboratories, providing a direct comparison between three analytical methods [micro-x-ray fluorescence spectroscopy (µ-XRF), solution analysis using inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma mass spectrometry]. Interlaboratory studies using glass standard reference materials and other glass samples were designed to (a) evaluate the analytical performance between different laboratories using the same method, (b) evaluate the analytical performance of the different methods, (c) evaluate the capabilities of the methods to correctly associate glass that originated from the same source and to correctly discriminate glass samples that do not share the same source, and (d) standardize the methods of analysis and interpretation of results. Reference materials NIST 612, NIST 1831, FGS 1, and FGS 2 were employed to cross-validate these sensitive techniques and to optimize and standardize the analytical protocols. The resulting figures of merit for the ICP-MS methods include repeatability better than 5% RSD, reproducibility between laboratories better than 10% RSD, bias better than 10%, and limits of detection between 0.03 and 9 µg g(-1) for the majority of the elements monitored. The figures of merit for the µ-XRF methods include repeatability better than 11% RSD, reproducibility between laboratories after normalization of the data better than 16% RSD, and limits of detection between 5.8 and 7,400 µg g(-1). The results from this study also compare the analytical performance of different forensic science laboratories conducting elemental analysis of glass evidence fragments using the three analytical methods.